Correlation between the structure of water in the vicinity of carboxybetaine polymers and their blood-compatibility

The structure and hydrogen bonding of water in the vicinity of carboxybetaine homopolymer (poly[1-carboxy-N,N-dimethyl-N-(2'-methacryloyloxyethyl)methanaminium inner salt] (PolyCMB), and a random copolymer of CMB and n-butyl methacrylate, Poly(CMB-r-BMA), with various molecular weights were analyzed in their aqueous solutions and thin film with contours of O-H stretching of Raman and attenuated total reflection infrared (ATR-IR) spectra, respectively. The relative intensity of the collective band (C value) corresponding to a long-range coupling of O-H stretchings of the Raman spectra for aqueous solution of Poly(CMB-r-BMA) was very close to that for pure water, which is in contrast with the smaller C value in aqueous solution of ordinary polyelectrolytes. The number of hydrogen bonds collapsed by the presence of one monomer residue (N(corr) value) of PolyCMB and Poly(CMB-r-BMA) (CMB, 45 mol %) (M(w), 1.14 x 10(4) and 1.78 x 10(4), respectively) could be calculated from the C value. The N(corr) values were much smaller than those for ordinary polyelectrolytes and close to those for nonionic water-soluble polymers such as poly(ethylene glycol) and poly(N-vinylpyrrolidone). Furthermore, a water-insoluble Poly(CMB-r-BMA) with a large BMA content (M(w) = 347 kD, CMB 27 mol %) could be cast as a thin film (thickness, ca. 10 microm) on a ZnSe crystal for the ATR-IR analyses. At an early stage of sorption of water into the Poly(CMB-r-BMA) film, the O-H stretching band of IR spectra for the water incorporated in the film was similar to that for free water, which is in contrast with the drastic change in the O-H stretching band of water incorporated in polymer films such as poly(methyl methacrylate) (PMMA) and poly(n-butyl methacrylate) (PBMA). The theoretical vibrational frequency for water molecules hydrating a betaine molecule calculated by using a density functional method supported the experimental results. The adhesion of human platelets to Poly(CMB-r-BMA) films was much less than that to PMMA and PBMA. With an increase in the content of CMB residue, the number of platelets adhered to the Poly(CMB-r-BMA) film drastically decreased and then gradually increased, probably due to the increase in the roughness of the film surface. These results suggest that the carboxybetaine monomer residues with a zwitterionic structure do not significantly disturb the hydrogen bonding between water molecules in both aqueous solution and thin film systems, resulting in the excellent blood-compatibility of the carboxybetaine polymers.     

A new synthesis of 1,3-dienes from allyl sulfides and allyl sulfones using tri-n-butylstannylmethyl iodide

Allyl 2-pyridyl sulfide $\text{6}$ or allyl phenyl sulfone $\text{7}$ on treatment with n-butyllithium in tetrahyrofuran followed by tri-n-butylstannylmethyl iodide ($\text{4}$) afforded directly the 1,3-diene $\text{8}$ in good yield.     

Synthesis, characterization and FET properties of novel dithiazolylbenzothiadiazole derivatives

Dithiazolylbenzothiadiazoles easily obtained have high electron affinity and the FET device of a trifluoromethylphenyl derivative exhibited a good n-type performance with high electron mobility.     

Optical microscopy and in situ Raman scattering of single crystalline ethylene hydrate and binary methane-ethylene hydrate at high pressures

Visual observations through a microscope and in situ Raman measurements have been made for single crystalline ethylene hydrate (EH) and binary methane-ethylene hydrate (MEH) at pressures up to 3.7 GPa and room temperature. Both hydrates showed pressure-induced phase transitions at 1.6, 2.0, and 3.0 GPa for EH and at 1.7, 2.1, and 3.3 GPa for MEH. The cubic sI phase of EH and MEH remains stable up to 1.6 and 1.7 GPa, respectively, which are more widely ranging values than the values for the methane hydrate sI phase. In this sI phase of binary MEH, the cage occupancies by methane and ethylene molecules are investigated from Raman spectra. Above P = 3.0 GPa for EH and 3.3 GPa for MEH, they decomposed by associating with the formation of the polyethylene.     

Photoinduced desorption of sulfur from gold nanoparticles loaded on metal oxide surfaces

We now report photoinduced sulfur desorption from the surfaces of Au nanoparticles loaded on metal oxides. This reaction occurs in water at ordinary temperature and pressure. Nanometer-sized Au particles have been formed on the surfaces of various metal oxides by deposition-precipitation (Au/oxides). Elemental sulfur (S8) is selectively adsorbed on the Au nanoparticle surfaces of Au/oxides in an atomic state at a coverage of (theta) 1/3. Irradiation (lambdaex > 300 nm) of the sulfur adsorbed Au/anatase TiO2 in water has led to reductive desorption of the sulfurs at room temperature. Electrochemical measurements using Au/oxides indicate that the driving force for this reaction is the photoinduced upward shift of Fermi energy of the metal oxide-supported Au nanoprticles. This study will open up a novel and wide application of heterogeneous photocatalysis for thermal catalysts.     

Smiles-type free radical rearrangement of aromatic sulfonates and sulfonamides: syntheses of arylethanols and arylethylamines

Smiles-type free radical rearrangements of arenesulfonates and arenesulfonamides are exploited for synthetic purposes. 4-Substituted benzenesulfonates cause Smiles-type rearrangement only when substituted by an electron withdrawing group. Therefore, ipso-attack by an alkyl radical on arenesulfonates takes place in an electrophilic manner. Arenesulfonamides rearrange only when the amide nitrogen is substituted by an alkoxycarbonyl group, due to the electron withdrawing nature of this group. Sulfonates and the N-ethoxycarbonylsulfonamide derivatives of naphthalene, quinoline, and thiophene cause more rearrangement and show synthetic utility. Aromatic amino acid analogues were synthesized by Smiles-type rearrangement with moderate yields. The radical Smiles-type rearrangement of sulfonate and sulfonamide derivatives can be a useful synthetic route when we understand the electronic character of these reactions.     

Development of hydrophilic fluorogenic derivatization reagents for thiols: 4-(N-acetylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole and 4-(N-trichloroacetylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole

Sensitive, reactive, and hydrophilic fluorogenic reagents for thiols with the benzofurazan skeleton, 4-(N-acetylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole (AcABD-F) and 4-(N-trichloroacetylaminosulfonyl)-7-fluoro-2,1,3-benzoxadiazole (TCAcABD-F) have been developed. These reagents reacted with thiols within 10 min at 60 degrees C. AcABD-F and TCAcABD-F themselves do not fluoresce but are strongly fluorescent after the reaction with thiol compounds. The generated derivatives were highly water-soluble, since they dissociated a proton and ionized in the neutral pH region. The derivatives with four biologically important thiol compounds were separated on a reversed-phase HPLC column and detected fluorometrically at 504 nm with excitation at 388 nm. The detection limit attained for homocysteine with AcABD-F was 25 fmol on column (11 nM) (signal-to-noise ratio = 3), and that for glutathione with TCAcABD-F was 45 fmol on column (20 nM).     

An automated analyzer for vancomycin in plasma samples by column-switching high-performance liquid chromatography with UV detection

An automated analyzer for vancomycin in rat plasma by column-switching high-performance liquid chromatography (HPLC) with UV detection was developed. The method includes in-line extraction of vancomycin by ion-exchange cartridge column and a separation on a reversed-phase column with UV detection at 215 nm. Plasma samples were diluted by mobile phase solution and directly injected to HPLC. Vancomycin was quantitatively recovered from rat plasma samples. The separation was completed within 15 min. The calibration curve was linear over the range from 0.5 to 100 microg/mL with the detection and quantification limits of 0.5 microg/mL (2.5 ng on column; signal-to-noise ratio = 3). The values of precision in intra- and inter-day assays (n = 3) were less than 1.92 and 3.69%, respectively. This method does not require time-consuming pre-treatment and is suitable for the routine assay of plasma samples.     

2-Chloroanthraquinone-catalyzed aerobic photo-oxidative synthesis of diacylamines from benzylamides

In this Letter, we report the aerobic photo-oxidative synthesis of diacylamines from benzylamides in the presence of molecular oxygen and catalytic amounts of 2-chloroanthraquinones under visible light irradiation from a fluorescent lamp.